In situ Fourier transform infrared spectroscopy was used to study the powder formation of
hexamethyldisiloxane/O2 plasmas. The spectra show that oxygen plays an important role at
the beginning of the process. A large amount of oxygen is responsible for intense powder
formation. The admixture of inert or non-reactant gases,
such as Ar or N2, into the plasma promotes polymeri-
zation of the monomer. The formation of the particulates,
the evolution of their size, and chemical characteristics
give evidence of a multistep growth process. The size, as
well as the production rate, undergoes a reduction once
the Ar or N2 amount is increased in the plasma admixture.
Experimental Part
Setup and Parameters
cm1
particle composition changes and particles mostly contain- mode, as well as the LO mode, seems to decrease once the
ing SiOx are found. It is presently supposed that the particles argon content is increased in the admixture, indicating a
undergo a dehydration or dehydroxylation. This mechan- reduction of the disorder degree. The carbon content,
ism is supported by a strong release of OH and the represented by the first right part of each spectrum (740
production of water as detected also by FTIR. The jump 880 cm1), decreases as the argon content increases; all the
visualized in the particle size behavior could be associated peaks related to Si(CH3)x vibrations tend to be smaller and
to a coalescence phase in particle evolution, during which smaller in amplitude, as well as the absorption band at
the size increases rapidly and at the same time the density 1 260 cm1 (related to Si(CH3)x stretching vibration) and
drops (Figure 1). Chemistry processes influence the plasma the CH3 symmetric and asymmetric stretching vibrations,
only in the first 40 s, after that we assisted to a rise of all the with the simultaneous appearance of a CH4 peak. CH4 is
species playing a role in the film and powder formation. formed by recombination of CH3 and H; when increasing
The effect of the introduction of argon into the gas argon, CH3 decreases and so there is the formation of CH4 at
admixture, by keeping a constant total flux is shown in high value of argon. Thus, a large argon amount limits the
Figure 6. increase of all the peaks containing carbon. In ref.[24] a
In all cases (O2/Ar ratio equal to 0.5, 1, and 2) the main reduced O2/HMDSO ration leads to an increase of carbon
vibrational lines in the in situ FTIR spectra remain the same, content; in our case we assisted to the contrary effect,
but their time evolution changes, as well as the light because the Ar ion has an energy threshold (13 eV) higher
scattering intensity (Figure 6). Rising the argon content than O ion (12 eV), and immediately react with the
leads to a clear decrease of all observed band integrals. The monomer, as explained later. They tend to be constant in
SiOSi stretching peak (or TO mode), for example, shifts to time; this is a clear indication of HMDSO polymerization. It
1 072 cm1, since due to the lower and lower oxygen clearly appears that the dissociation, polymerization and
presence in the admixture; anyway the shift is not particle growth processes are strongly dependant on the
significant, due to used resolution. In addition, the TO dilution ratio of HMDSOO2Ar.
The time evolution of each peak (Figure 7) reveals that the
process of the particle formation is dominated by the
polymerization of the monomer, because each band
integral is more or less constant in time. The polymerization
process influences the powder particle size; their radius
does not modify significantly.
In Figure 8 it is shown that the radius becomes smaller
and smaller, once the O2/Ar ratio in gas admixture is
reduced. Thus, a higher presence of argon limits the powder
particles formation and growth, as we can notice from the
evolution of the light scattering intensity. The powder
nm
3
H2 Sg 3 Su primary system 200320
G 1
S 1
g B Su G !B 453464
d 3
Pu a3 S
g Fulcher-a 580650
2 2
CH A D X P 4 300 A system 431.4 (0,0)
2
B2 SX P 3 900 A system 388.9, 387.1 (0,0)
Ha n(>2) ! n 2 (Balmer line) 656.3
N2 C3 Pu B3 Pg second positive
CO Kaplan bands 252, 275
b3 Sa3 P third positive 283370
and 5B Bands 266383
Q
d3~ a3 triplet bands 401647
1 1 451608
B SA P angstrom system
03 1 575800
a Sa P asundi bands
CO B2 SX2 S first negative system 255315
2 2 309640
A PX S comet-tail system
CO
2
2 2
A S X P ll 2 883 and 2 896 288.3, 289.6
Ar 750.4, 751.1, 763.5, 772.3, 772.4
O 3s 5S8-3p 5P 777.2, 777.4, 777.5
bonds. Also in the case of N2, the time evolution of the Ex Situ Measurements of Collected Powder and
principal bands (H2, CH, and N2) are reduced in intensity; Deposited Films
the reduction is consistent in case of low N2 content, related
to the particle growth. The ex situ ATR-FTIR spectra of collected powder particles,
for different HMDSOO2Ar and HMDSOO2N2 admix-
tures, are shown in Figure 14a and b. The vibrational modes
are the same as previously described in Table 1. The SiOSi
stretching peak (or TO mode) at 1 075 cm1, found for
low O2/Ar or O2/N2 ratios, shifts to 1 072 cm1, because of
the oxygen reduction in the admixture; the decrease of the
stoichiometry in SiOx is more efficient. In addition, the TO
mode, as well as the LO mode, seem to decrease once the
argon or nitrogen content is increased in the admixture,
confirming a reduction in disorder degree of the layers. The
carbon content, represented by the first right part of each
spectrum (700800 cm1), decreases as the Ar (or N2)
content increases; all the peaks related to Si(CH3)x vibra-
tions tend to reduce in amplitude, as well as the Si(CH3)x
stretching vibration at 1 260 cm1 and the CH3 symmetric
and asymmetric stretching vibrations. The powder chem-
Figure 13. Time evolution of the line intensity of principal optical istry is quite similar to the plasma phase chemistry; in both
lines in the HMDSOO2Ar plasma. cases a large amount of argon or nitrogen reduces carbon
Figure 14. (a) Absorbance spectra of powder particles produced in HMDSOO2N2 plasmas with different O2/N2 ratio (f O2/N2).
(b) Absorbance spectra of powder particles produced in HMDSOO2Ar plasmas with different O2/Ar ratio (f O2/Ar).
Conclusion
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